Acyloxylation of different types of enol ethers (derived from aldehydes and ketones) by dimethyl peroxydicarbonate (DPDC) results in either addition to the double bond or in a formal replacement of an allylic hydrogen by a methoxycarbonyloxy group forming vicinal oxygenated hydrocarbons. 1,3-oxygenated products via monoacyloxylation could not be observed. The results with 1-methoxycyclohex-1-ene (1a) are compared with copper(I)-salt catalyzed acyloxylations by means of tert. butyl peroxycarboxylates 2a, b.